New direct-dyeing azo-dyestuffs and process for their manufacture



W DIRECT-DYEING AZO-DYESTUFFS AND PROCESS FOR THEIR MANUFACTURE HenriRiat, Arlesheim, Switzerland, assignor to Ciba Limited, Basel,Switzerland, a Swiss firm No Drawing. Application May 20, 1957 goodresults obtained therewith there come into consideration more especiallysulfonic acids of 2-(4'-aminophenyl)-6-methyl-benzthiazole, for example,the 2-(4'- aminophenyl)-6-methy1-benzthiazole-x-sulphonic acidobtainable by sulfonating 2-(4-aminophenyl)-6-methyl* benzthiazole withconcentrated sulfuric acid, or 2-('4'- aminophenyl) 6 methylbenzthiazole 3' sulfonic acid which is obtainable by thermalrearrangement of the acid sulfate of2-(4'-aminophenyl)-6-methyl-benzthiazole. Especially advantageousaredisulfonic acids, serial for example, the disulfonic acidof theformula 7 Claims. (Cl. 260-158) (8) s i H.0- r p a oONH, This inventionprovides new direct-dyeing azo-dyes stuffs which like, for example, thedisazo-dyestufl of the H038 r formula t which is obtainable by thethermal rearrangement of, (1) a s a a s Hio-- CH:

0ON=N NH-Cf-HNONENOO Hots s 0311 I H085 a 80m HN-0 C-CH:

HkQ-CO-NH correspondto the formula a a R1-N=N-RrNH--(%- OH=OH IOHN-R'i-N=N--Ri V I b L 6Jm-h V in which R and R each represents theradical of a 2-phenyl-(1')-benzthiazole bound in that-position to theazo linkage and containing at least one sulfonic acid group, R and Reach represents, a benzene radical which is bound in the 4-position tothe NH group and in the 1-position to the am linkage and contains in the2-position an acylamino group, and m represents a whole number notgreater than 2. i i

The invention also provides a process for the manufacture of the newdyestufis of the Formula 2 wherein dyestuffs of the formula in which Rand R have the meanings given above, are

linked together by means of a compound of the formula Halogen-F++CH=CH-C-Halogen in which m represents a whole number not greater thanazo-dyestufis of the Formula 4 diam-components con-' taining at leastonesulfonic acid group andhaving the formula in which R represents 'abenzene radial fused on in the manner shown to the thiazole ring, and R"represents a benzene radical to which the amino group is bound inpara-position the bond connecting it to the thiazole ring, atleasVone'oi the benzene radicals containing a sol-ionic acid group and,it desired, both benzene radicals,

may contain further substituents 'for example, halogen atoms such aschlorine, methoxy or ethoxy groups. 0wing to theease with which they can'be obtained and the the acid sulfate of the, monosulfonic acidobtainable by sulfonating 2 (4', aminophenyl.) 6 methyl 7 benzthiazolewith concentrated sulfuric acid. I

The diazotized 2-(4f-aminophenyl)-benzthiazoles con; taining a sulfonicacid group are coupled with l-amino 3-acylaminobenzenes. The latter maycontain, especially in the o-p'osition, further substituents, forexample alkyl or alkoxy groups of low molecular weight such as methyl,ethyl, methoxy or ethoxy groups. The acyle amino group in the 3-positionis advantageously derived from a carboxylic acid of low molecularweight, for ex-r ample, it may be a formylamino, acetylamino, propionyleamino, hydroxyacetylamino, hydroxypropionylamino or H NCO-group.Accordingly, there may be used with advantage, for example,.1-amino-3-acylamino benzenes of the formula Zo0l{TH g in which Yrepresents a hydrogen atom or an alkyl or alkoxy group of low molecularweight, and Z represents an ethyl or hydroxymethyl group but especiallya methyl group or an H N-group. As examples of l-amino-3-acylaminobenzenes of the Formula 7 there may be mentionedl-amino-3:acetylamino-benzene, 1-amino-3-propionylaminobenzene,l-amino-3-hydroxyacetyI-aminoben zone, 1 amino 3 acetylamino 6methoxybenzene, (3-amino-phenyl)-urea and (B-aminol-methoxyphenyl) urea.r .t

The diazotized 2-(4-aminophenyl)-benzthiazolesr may be coupled with the1-amino-3-acylaminobenzenes'lin the; usual manner, and advantageously ina weakly acid. to neutral, for example, acetic acid, medium. In theprocess of this invention the amino-monoazo dyestuffs so obtained arelinked together by means of an acid halide of the Formula 3, for.example, furnaric .acid dichloride or advantageously phosgene, to formthe disazo-dyestutfs. For this purpose, for example, equimolecularproportions of two diiferent amino-monoazodyestufis, which are both ofthe Formula 4, arereacted with phosgene, or by reacting a singleamino-inonoazotained contains an average of at least three sulfonic acidan agent capable of binding acid, such as an alkali metal carbonate. Thenew dyestufis of the Formula 2 are suitable for dyeing or printing avery wide variety of materials, especially those of animal origin, suchas wool, silk or leather, but especially cellulosic fibers such aslinen, cotton, and artificial silk or staple fibers or regeneratedcellulose. The new dyestuffs possess an especially good affinity for thelatter fibers and they yield level tints having good properties offastness. The new dyestufis yield on cellulosic fibers. dyeings whichcan be discharged very well not only by means of the known neutraldischarge pastes containing sodium formaldehyde-sulfoxylate, but alsowith the usual alkaline discharge pastes containing sodiumformaldehyde-sulfoxylate.

The following examples illustrate the invention, the parts andpercentages being by weight:

Example 1 The diazo compound prepared from 40 parts of 2-(4-aminophenyl)-6-methyl-benzthiazole-3-x-disulfonic acid(dehydrothiotoluidine disulfonic acid) in the usual manner is coupled inan acetic acid solution with parts of 1-arnino-3-acetylaminobenzene. Themonoazo-dyestutf so obtained can be. purified by reprecipitation. It isdissolved in 3000 parts of water and the solution is treated at 40- 60,C. with phosgene untilaminoazo-dyestuif can no longer be detected, thereaction mixture being maintained weakly alkaline by the addition ofsodium carbonate. The precipitated dyestufi is filtered off and dried.It dissolves in water to give a yellow-orange coloration and dyes cottonorange tints which are fast to light. The dyeings are dischargeable towhite.

"By using as azo-component for preparing the monoazodyestufi, instead of1-amino-3-acetylaminobenzene, 15 parts of (3-aminophenyl)-urea, there isobtained a dyestufi' which dyes cotton redder tints. Furtherdisazodyestuffs which dye cotton orange tints are obtained by using ascoupling components for preparing the aminomonoazo-dyestutf1-amino-3-propionylaminobenzene, l-

CHI

amino-3-hydroxyacetylaminobenzene or 1-amino-3 -acety1- amino-6-methylbenzene. Finally, by using, instead of l-amino-3-acetylarninobenzene,the corresponding quantity of 1-amino-3-acetylamino-6-methoxybenzene or(3- amino-4-methoxyphenyl)-urea, there are obtained dyestufis which dyecotton dull red tints.

Example 2 28 parts of the amino-azo-dyestutf described in the CH S\O N'NR NHG |-IQHCHI C HN R N-N H a "if first paragraph of Example 1 aredissolved in 4000 parts of water together with 24 parts of theazo-dyestufi obtained from diazotizcd 2-(4.-aminophenyl)-6-methylbenzthiazole-x-sulfonic acid and 1-amino-3-acetylarhinobenzene,and treated with phosgene in the manner described in Example 1 until theamino group can no longer be detected. The dyestuff so obtained dyescotton yelloworange tints.

A similar dyestufi is obtained when 28 parts of the amino-azo-dyestufldescribed in the first paragraph of Example 1 and 24 "parts of theamino-azo-dycstuff obtained from diazotizcd 2-(4'-aminophenyl)-6-rneth'yl-benzthiazole-x-sulfonic acid and (3-aminophenyl)-urea aredissolved in 4000 parts of water and treated with phosgene in the mannerdescribed in Example 1.

' Example 3 40 parts of the monoazo-dyestuff described in the firstparagraph of Example 1 are dissolved in'3000parts of water, and treatedwith furnaric acid dichloride at a-temperature of 30-40 C. until no freeamino groupcanbe detected in the reaction mixture. The mineral acid setfree during the condensation is neutralized by the gradual addition ofsodium carbonate or sodium hydroxide. The disazo-dyestuir" so formed isfiltered off and dried. It dyes cotton yellow-orange tints.

Example 4 100 parts of cotton satin are introduced at C.,into a dyebathwhich contains in 3000 parts of water 1.5 parts of the disazo-dyestuflobtained as described in thefirst paragraph of Example 1 and 2 parts of'trisodium phosphate, and the whole is heated to -95 C., and after hour30 parts of crystalline sodium sulfate are added, and then dyeing iscontinued for hour at about C. The material is then rinsed in the coldand dried. The cotton is dyed an orange tint. I

On the cotton satin dyed in this manner pure white discharge prints canbe made by means of the alkaline discharge printing paste of thefollowing composition;

1000 parts What is claimed is: 1. A disazo dyestuff of the formula 60 inwhich k, m and n each represent a whole number of at 65 bound to thebenzene ring 5 in which E, m and n each represent a whole number of bythe nitrogen atom of its NH-CO- grouping and at least I and at the most2, and R represents a benzene which contains at the most 3 carbon atoms.

radical bound in the 4-position of the -NH- group and 4. A disazodyestufi' of the formula 5 s N=N R, NH.C HN R, N=N@/ H S DE 3 1103 s Ns0,H

in the 1-position to the azo linkage and containing in the in which Rrepresents a benzene radical bound in the 2-position an acylamino groupwhich is bound to the 4-position to the --NH-group and in the 1-positionto the benzene ring by the nitrogen atom of its -NH-CO azo linkage andcontaining in the 2-position an acylamino grouping and which contains atthe most 3 carbon atoms. group which is bound to the benzene ring by thenitrogen 3. A disazo dyestutf of the formula atom of its -NHCO groupingand which contains at s s H": 26gN=NRr-NH-fi l:cH=CH-Ei?N-RrN==N-O CH,HO;S 01H HO|S N son in which m represents a whole number of at least 1and at the most 2 and R, represents a benzene radical bound the most 3carbon atoms. in the 4-position to the -NH- group and in the l-posi- S.The disazo dyestufi of the formula tion to the azo linkage andcontaining in the 2-positi0n 6. The disazo dyestuif of the formula 11,0j on,

an aeylamino group which is bound to the benzene ring 7. The disazodyestufi of the formula s OH:

0 N==N Nn-o-rrN N=NOO C 8 g om HN-O oom H,o0c-Nn |H References Cited inthe file of this patent UNITED STATES PATENTS 2,384,283 Conrad et al.Sept. 4, 1945

1. A DISAZO DYESTUFF OF THE FORMULA